Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/0402—Methods of deposition of the material
  • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
  • H01M4/622—Binders being polymers
  • H01M4/623—Binders being polymers fluorinated polymers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/134—Electrodes based on metals, Si or alloys
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—Processes of manufacture
  • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—Processes of manufacture
  • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
  • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
  • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
  • H01M4/622—Binders being polymers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/624—Electric conductive fillers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/624—Electric conductive fillers
  • H01M4/625—Carbon or graphite
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/64—Carriers or collectors
  • H01M4/66—Selection of materials
  • H01M4/661—Metal or alloys, e.g. alloy coatings
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/64—Carriers or collectors
  • H01M4/70—Carriers or collectors characterised by shape or form
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
  • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
  • H01G11/22—Electrodes
  • H01G11/30—Electrodes characterised by their material
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the disclosure relates to fluoropolymer binder compositions and slurries that could be used in manufacturing electrodes for use in electrical storage devices, such as batteries.
• PVDF fluoropolymer because of their excellent electrochemical resistance, have been found to be useful binders for forming electrodes to be used in electrical storage devices.
• the PVDF fluoropolymer is dissolved in an organic solvent and the electrode material is combined with the solution to form a slurry that is applied to a metal foil or mesh to form the electrode.
• the role of the organic solvent is to dissolve the fluoropolymer in order to provide good adhesion between the electrode material particles and the metal foil or mesh upon evaporation of the organic solvent.
• the organic solvent of choice is N-methyl-2-pyrrolidone (NMP).
• NMP N-methyl-2-pyrrolidone
• PVDF binders dissolved in NMP provide superior adhesion and an interconnectivity of all the active ingredients in the electrode composition.
• the bound ingredients are able to tolerate large volume expansion and contraction during charge and discharge cycles without losing interconnectivity within the electrodes.
• Interconnectivity of the active ingredients in an electrode is extremely important in battery performance, especially during charging and discharging cycles, as electrons must move through the electrode, and lithium ion mobility requires interconnectivity within the electrode between particles.
• NMP is a toxic material and presents health and environmental issues.
• Fig. 1 is a graph showing the viscosity at a range of shear rates of positive electrode slurry compositions prepared in the Examples section and shows the viscosity at a range of shear rates for an initial sample and an aged sample.
• Fig. 2 is a graph showing rheology measurements showing viscosity at 10 s 1 shear rate for binders prepared in the Examples section.
• the present disclosure provides a binder composition
• a binder composition comprising: (a) at least one fluoropolymer comprising the residue of vinylidene fluoride; and (b) one or more (meth)acrylic polymers comprising constitutional units comprising the residue of: (i) 40% to 80% by weight of an alkyl ester of (meth)acrylic acid containing from 1 to 3 carbon atoms in the alkyl group; (ii) 18% to 48% by weight of an alkyl ester of (meth)acrylic acid containing from 4 to 18 carbon atoms in the alkyl group; (iii) 0.1% to 10% by weight of a hydroxyalkyl ester; (iv) 0% to 10% by weight of an alpha, beta-ethylenically unsaturated carboxylic acid; and (v) 0% to 20% by weight of an ethylenically unsaturated monomer comprising a heterocyclic group, the % by weight based on the total monomer weight that comprise
• the present disclosure also provides a slurry composition
• a slurry composition comprising: a binder composition comprising: (a) at least one fluoropolymer comprising the residue of vinylidene fluoride; and (b) one or more (meth)acrylic polymers comprising constitutional units comprising the residue of: (i) 40% to 80% by weight of an alkyl ester of (meth)acrylic acid containing from 1 to 3 carbon atoms in the alkyl group; (ii) 18% to 48% by weight of an alkyl ester of (meth)acrylic acid containing from 4 to 18 carbon atoms in the alkyl group; (iii) 0.1% to 10% by weight of a hydroxyalkyl ester; (iv) 0% to 10% by weight of an alpha, beta-ethylenically unsaturated carboxylic acid; and (v) 0% to 20% by weight of an ethylenically unsaturated monomer comprising a heterocyclic group, the % by
• the present disclosure further provides a slurry composition
• a binder composition comprising: (a) at least one fluoropolymer comprising the residue of vinylidene fluoride; and (b) one or more (meth)acrylic polymers comprising constitutional units comprising the residue of: (i) 40% to 80% by weight of an alkyl ester of (meth)acrylic acid containing from 1 to 3 carbon atoms in the alkyl group; (ii) 18% to 48% by weight of an alkyl ester of (meth)acrylic acid containing from 4 to 18 carbon atoms in the alkyl group; (iii) 0.1% to 10% by weight of a hydroxyalkyl ester; (iv) 0% to 10% by weight of an alpha, beta-ethylenically unsaturated carboxylic acid; and (v) 0% to 20% by weight of an ethylenically unsaturated monomer comprising a heterocyclic group, the % by weight based on the
• the present disclosure also provides an electrode comprising: (A) an electrical current collector; and (B) a film on the electrical current collector, wherein the film comprises:
• an electrochemically active material and (2) a binder comprising: (a) at least one fluoropolymer comprising the residue of vinylidene fluoride; and (b) one or more (meth)acrylic polymers comprising constitutional units comprising the residue of: (i) 40% to 80% by weight of an alkyl ester of (meth)acrylic acid containing from 1 to 3 carbon atoms in the alkyl group; (ii) 18% to 48% by weight of an alkyl ester of (meth)acrylic acid containing from 4 to 18 carbon atoms in the alkyl group; (iii) 0.1% to 10% by weight of a hydroxyalkyl ester; (iv) 0% to 10% by weight of an alpha, beta-ethylenically unsaturated carboxylic acid; and (v) 0% to 20% by weight of an ethylenically unsaturated monomer comprising a heterocyclic group, the % by weight based on the total monomer weight that comprise the one or
• the present disclosure further provides an electrical storage device comprising:
• an electrode comprising: (A) an electrical current collector; and (B) a film on the electrical current collector, wherein the film comprises: (1) an electrochemically active material; and (2) a binder comprising: (a) at least one fluoropolymer comprising the residue of vinylidene fluoride; and (b) one or more (meth)acrylic polymers comprising constitutional units comprising the residue of: (i) 40% to 80% by weight of an alkyl ester of (meth)acrylic acid containing from 1 to 3 carbon atoms in the alkyl group; (ii) 18% to 48% by weight of an alkyl ester of (meth)acrylic acid containing from 4 to 18 carbon atoms in the alkyl group; (iii) 0.1% to 10% by weight of a hydroxyalkyl ester; (iv) 0% to 10% by weight of an alpha, beta-ethylenically unsaturated carboxylic acid; and (v) 0% to 20% by weight of an ethy
• the present disclosure is directed to a binder composition
• a binder composition comprising: (a) at least one fluoropolymer comprising the residue of vinylidene fluoride; and (b) one or more (meth)acrylic polymers comprising constitutional units comprising the residue of: (i) 40% to 80% by weight of an alkyl ester of (meth)acrylic acid containing from 1 to 3 carbon atoms in the alkyl group; (ii) 18% to 48% by weight of an alkyl ester of (meth)acrylic acid containing from 4 to 18 carbon atoms in the alkyl group; (iii) 0.1% to 10% by weight of a hydroxyalkyl ester; (iv) 0% to 10% by weight of an alpha, beta-ethylenically unsaturated carboxylic acid; and (v) 0% to 20% by weight of an ethylenically unsaturated monomer comprising a heterocyclic group, the % by weight based on the total monomer weight
• the binder composition comprises a fluoropolymer.
• the fluoropolymer may comprise a (co)polymer comprising the residue of vinylidene fluoride.
• a non-limiting example of a (co)polymer comprising the residue of vinylidene fluoride is a polyvinylidene fluoride polymer (PVDF).
• PVDF polyvinylidene fluoride polymer
• the “polyvinylidene fluoride polymer” includes homopolymers, copolymers, such as binary copolymers, and terpolymers, including high molecular weight homopolymers, copolymers, and terpolymers.
• Such (co)polymers include those containing at least 50 mole percent, such as at least 75 mole %, and at least 80 mole %, and at least 85 mole % of the residue of vinylidene fluoride (also known as vinylidene difluoride).
• vinyl halide monomers such as trifluoroethylene, chlorotrifluoroethylene, hexafluoropropen
• the fluoropolymer may also comprise a PVDF homopolymer.
• the fluoropolymer may have a weight average molecular weight of at least 50,000 g/mol, such as at least 100,000 g/mol, such as at least 250,000 g/mol, such as at least 300,000 g/mol, such as at least 350,000 g/mol, such as at least 400,000 g/mol, such as at least 450,000 g/mol, such as at lest 500,000 g/mol, such as at least 550,000 g/mol, such as 600,000 g/mol, such as at least 650,000 g/mol, such as at least 700,000 g/mol, such as at least 750,000 g/mol, such as at least 800,000 g/mol, such as at least 850,000 g/mol, such as at least 900,000 g/mol, such as at least 950,000 g/mol, such as at least 1,000,000 g/mol, such as at least 1,050,000 g/mol, such as
• the fluoropolymer may have a weight average molecular weight of no more than 1,500,000 g/mol, such as no more than 1,250,000 g/mol, such as no more than 1,200,000 g/mol, such as no more than 1,150,000 g/mol, such as no more than 1,100,000 g/mol, such as no more than 1,050,000 g/mol, such as no more than 1,000,000 g/mol, such as no more than 950,000 g/mol, such as no more than 900,000 g/mol, such as no more than 850,000 g/mol, such as no more than 800,000 g/mol, such as no more than 750,000 g/mol, such as no more than 700,000 g/mol, such as no more than 650,000 g/mol, such as no more than 600,000 g/mol, such as no more than 550,000 g/mol, such as no more than 500,000 g/mol, such as no more than 450,000 g/mol, such as no more than 400,000 g/mol,
• the fluoropolymer may have a weight average molecular weight of 50,000 to 1,500,000 g/mol, such as 250,000 to 700,000 g/mol, such as 250,000 to 650,000 g/mol, such as 250,000 to 600,000 g/mol, such as 250,000 to 550,000 g/mol, such as 250,000 to 500,000 g/mol, such as 250,000 to 450,000 g/mol, such as 250,000 to 400,000 g/mol, such as 250,000 to 350,000 g/mol, such as 250,000 to 300,000 g/mol, such as 300,000 to 700,000 g/mol, such as 300,000 to 650,000 g/mol, such as 300,000 to 600,000 g/mol, such as 300,000 to 550,000 g/mol, such as 300,000 to 500,000 g/mol, such as 300,000 to 450,000 g/mol, such as 300,000 to 400,000 g/mol, such as 300,000 to 350,000 g/mol, such as such as 350,000 to 700,
• PVDF is commercially available, e.g., from Arkema under the trademark KYNAR from Solvay under the trademark HYLAR, and from Inner Mongolia 3F Wanhao Fluorochemical Co., Ltd.
• the fluoropolymer used in preparing the binder may comprise a nanoparticle.
• nanoparticle refers to particles having a particle size of less than 1,000 nm.
• the fluoropolymer may have a particle size of at least 50 nm, such as at least 100 nm, such as at least 250 nm, such as at least 300 nm, and may be no more than 900 nm, such as no more than 600 nm, such as no more than 450 nm, such as no more than 400 nm, such as no more than 300 nm, such as no more than 200 nm.
• the fluoropolymer nanoparticles may have a particle size of 50 nm to 900 nm, such as 100 nm to 600 nm, such as 250 nm to 450 nm, such as 300 nm to 400 nm, such as lOOnm to 400 nm, such as 100 nm to 300 nm, such as 100 nm to 200 nm.
• particle size refers to average diameter of the fluoropolymer particles.
• the particle size referred to was determined by the following procedure: A sample was prepared by dispersing the fluoropolymer onto a segment of carbon tape that was attached to an aluminum scanning electron microscope (SEM) stub. Excess particles were blown off the carbon tape with compressed air. The sample was then sputter coated with Au/Pd for 20 seconds and was then analyzed in a Quanta 250 FEG SEM (field emission gun scanning electron microscope) under high vacuum. The accelerating voltage was set to 20.00 kV and the spot size was set to 3.0. Images were collected from three different areas on the prepared sample, and ImageJ software was used to measure the diameter of 10 fluoropolymer particles from each area for a total of 30 particle size measurements that were averaged together to determine the average particle size.
• SEM aluminum scanning electron microscope
• the fluoropolymer may be present in in the binder in amounts of at least 40% by weight, such as at least 50% by weight, such as at least 60% by weight, such as at least 70% by weight, such as at least 80% by weight, such as at least 85% by weight, such as at least 90% by weight, such as at least 95% by weight, such as at least 98% by weight, based on the total weight of the binder solids.
• the fluoropolymer may be present in in the binder in amounts of no more than 99% by weight, such as no more than 98% by weight, such as no more than 96% by weight, such as no more than 95% by weight, such as no more than 90% by weight, such as no more than 85% by weight, such as no more than 80% by weight, based on the total weight of the binder solids.
• the fluoropolymer may be present in in the binder in amounts of 40% to 99% by weight, such as 40% to 98% by weight, such as 40% to 96% by weight, such as 40% to 95% by weight, such as 40% to 90% by weight, such as 40% to 85% by weight, such as 40% to 80% by weight, such as 50% to 99% by weight, such as 50% to 98% by weight, such as 50% to 96% by weight, such as 50% to 95% by weight, such as 50% to 90% by weight, such as 50% to 85% by weight, such as 50% to 80% by weight, such as 60% to 99% by weight, such as 60% to 98% by weight, such as 60% to 96% by weight, such as 60% to 95% by weight, such as 60% to 90% by weight, such as 60% to 85% by weight, such as 60% to 80% by weight, such as 70% to 99% by weight, such as 70% to 98% by weight, such as 70% to 96% by weight, such as 70% to 95% by weight, such as 70% to 90% by weight, such as 60% to 85% by weight
• the binder composition and/or slurry composition further comprise a
• the binder composition and/or slurry composition may comprise one, two, three, four or more different (meth)acrylic polymers.
• the (meth)acrylic polymer may be in the form of a block polymer, a random polymer, or a gradient polymer.
• the (meth)acrylic may comprise functional groups.
• the functional groups may comprise, for example, active hydrogen functional groups, heterocyclic groups, and combinations thereof.
• active hydrogen functional groups refers to those groups that are reactive with isocyanates as determined by the Zerewitinoff test described in the JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Vol. 49, page 3181 (1927), and include, for example, hydroxyl groups, primary or secondary amino groups, carboxylic acid groups, and thiol groups.
• heterocyclic group refers to a cyclic group containing at least two different elements in its ring such as a cyclic moiety having at least one atom in addition to carbon in the ring structure, such as, for example, oxygen, nitrogen or sulfur.
• heterocylic groups include epoxides, aziridines, thioepoxides, lactams and lactones.
• epoxide functional groups when epoxide functional groups are present on the (meth)acrylic polymer, the epoxide functional groups on the (meth) acrylic polymer optionally may be post- reacted with a beta-hydroxy functional acid.
• Non-limiting examples of beta-hydroxy functional acids include citric acid, tartaric acid, and/or an aromatic acid, such as 3-hydroxy-2-naphthoic acid.
• the ring opening reaction of the epoxide functional group will yield hydroxyl functional groups on the (meth)acrylic.
• the (meth)acrylic polymer may comprise constitutional units comprising the residue of one or more (meth)acrylic monomers.
• the (meth)acrylic polymer may be prepared by polymerizing a reaction mixture of alpha, beta-ethylenically unsaturated monomers that comprise one or more (meth)acrylic monomers and optionally other ethylenically unsaturated monomers.
• (meth) acrylic monomer refers to acrylic acid, methacrylic acid, and monomers derived therefrom, including alkyl esters of acrylic acid and methacrylic acid, and the like.
• (meth) acrylic polymer refers to a polymer derived from or comprising constitutional units comprising the residue of one or more (meth)acrylic monomers.
• the mixture of monomers may comprise one or more active hydrogen group- containing (meth)acrylic monomers, ethylenically unsaturated monomers comprising a heterocyclic group, and other ethylenically unsaturated monomers.
• the (meth)acrylic polymer may also be prepared with an epoxy functional ethylenically unsaturated monomer such as glycidyl methacrylate in the reaction mixture, and epoxy functional groups on the resulting polymer may be post-reacted with a beta-hydroxy functional acid such as citric acid, tartaric acid, and/or 3-hydroxy-2-naphthoic acid to yield hydroxyl functional groups on the (meth)acrylic polymer.
• an epoxy functional ethylenically unsaturated monomer such as glycidyl methacrylate
• epoxy functional groups on the resulting polymer may be post-reacted with a beta-hydroxy functional acid such as citric acid, tartaric acid, and/or 3-hydroxy-2-naphthoic acid to yield hydroxyl functional groups on the (meth)acrylic polymer.
• the (meth)acrylic polymer may comprise constitutional units comprising the residue of an alkyl esters of (meth)acrylic acid containing from 1 to 3 carbon atoms in the alkyl group.
• alkyl esters of (meth)acrylic acid containing from 1 to 3 carbon atoms in the alkyl group include methyl (meth)acrylate and ethyl (meth) acrylate.
• the constitutional units comprising the residue of the alkyl esters of (meth)acrylic acid containing from 1 to 3 carbon atoms in the alkyl group may comprise at least 30% by weight, such as at least 35% by weight, such as at least 40% by weight, such as at least 45% by weight, such as at least 47.5% by weight, based on the total weight of the (meth)acrylic polymer.
• the constitutional units comprising the residue of the alkyl esters of (meth)acrylic acid containing from 1 to 3 carbon atoms in the alkyl group may comprise no more than 96%, such as no more than 90%, such as no more than 85%, such as no more than 80%, such as no more than 75%, such as no more than 70%, such as no more than 65%, based on the total weight of the (meth)acrylic polymer.
• the constitutional units comprising the residue of the alkyl esters of (meth)acrylic acid containing from 1 to 3 carbon atoms in the alkyl group may comprise 30% to 96% by weight, such as 30% to 90% by weight, such as 30% to 85% by weight, such as 30% to
• 70% by weight such as 35% to 65% by weight, such as 40% to 96% by weight, such as 40% to
• the (meth)acrylic polymer may be derived from a reaction mixture comprising the alkyl esters of (meth)acrylic acid containing from 1 to 3 carbon atoms in the alkyl group in an amount of 30% to 96% by weight, such as 30% to 90% by weight, such as 30% to 85% by weight, such as 30% to 80% by weight, such as 30% to 75% by weight, such as 30% to
• 70% by weight such as 30% to 65% by weight, such as 35% to 96% by weight, such as 35% to
• the (meth)acrylic polymer may comprise constitutional units comprising the residue of an alkyl esters of (meth)acrylic acid containing from 4 to 18 carbon atoms in the alkyl group.
• Non-limiting examples of alkyl esters of (meth)acrylic acid containing from 4 to 18 carbon atoms in the alkyl group include butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, isodecyl (meth)acrylate, stearyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth) acrylate and dodecyl (meth) acrylate.
• the constitutional units comprising the residue of the alkyl esters of (meth)acrylic acid containing from 4 to 18 carbon atoms in the alkyl group may comprise at least 2% by weight, such as at least 5% by weight, such as at least 10% by weight, such as at least 15% by weight, such as at least 18% by weight, such as at least 18% by weight.
• the constitutional units comprising the residue of the alkyl esters of (meth)acrylic acid containing from 4 to 18 carbon atoms in the alkyl group may comprise no more than 60% by weight, such as no more than 50% by weight, such as no more than 45% by weight, such as no more than 40% by weight, such as no more than 35% by weight, based on the total weight of the (meth)acrylic polymer.
• the constitutional units comprising the residue of the alkyl esters of (meth)acrylic acid containing from 4 to 18 carbon atoms in the alkyl group may comprise 2% to 60% by weight, such as 2% to 50% by weight, such as 2% to 45% by weight, such as 2% to 40% by weight, such as 2% to 35% by weight, such as 5% to 60% by weight, such as 5% to 50% by weight, such as 5% to 45% by weight, such as 5% to 40% by weight, such as 5% to 35% by weight, such as 10% to 60% by weight, such as 10% to 50% by weight, such as 10% to 45% by weight, such as 10% to 40% by weight, such as 10% to 35% by weight, such as 15% to 60% by weight, such as 15% to 50% by weight, such as 15% to 45% by weight, such as 15% to 40% by weight, such as 15% to 35% by weight, such as 18% to 60% by weight, such as 18% to 50% by weight, such as 18% to 45% by weight, such as 18% to 40% by weight, such
• the (meth)acrylic polymer may be derived from a reaction mixture comprising the alkyl esters of (meth)acrylic acid containing from 4 to 18 carbon atoms in the alkyl group in an amount of % to 60% by weight, such as 2% to 50% by weight, such as 2% to 45% by weight, such as 2% to 40% by weight, such as 2% to 35% by weight, such as 5% to 60% by weight, such as 5% to 50% by weight, such as 5% to 45% by weight, such as 5% to 40% by weight, such as 5% to 35% by weight, such as 10% to 60% by weight, such as 10% to 50% by weight, such as 10% to 45% by weight, such as 10% to 40% by weight, such as 10% to
• 35% by weight such as 15% to 60% by weight, such as 15% to 50% by weight, such as 15% to
• 40% by weight such as 18% to 35% by weight, such as 20% to 60% by weight, such as 20% to
• 50% by weight such as 20% to 45% by weight, such as 20% to 40% by weight, such as 20% to
• the (meth)acrylic polymer may comprise constitutional units comprising the residue of a hydroxyalkyl ester.
• hydroxyalkyl esters include hydroxyethyl (meth) acrylate and hydroxypropyl (meth)acrylate.
• the constitutional units comprising the residue of the hydroxyalkyl ester may comprise at least 0.5% by weight, such as at least 1% by weight, such as at least 1.5% by weight, based on the total weight of the (meth)acrylic polymer.
• the constitutional units comprising the residue of the hydroxyalkyl ester may comprise no more than 20% by weight, such as no more than 15% by weight, such as no more than 8% by weight, such as no more than 6% by weight, such as no more than 5% by weight, such as no more than 4% by weight, such as no more than 3% by weight, such as no more than 2% by weight, such as no more than 1.5% by weight, such as no more than 1.0% by weight, based on the total weight of the (meth)acrylic polymer.
• the constitutional units comprising the residue of the hydroxyalkyl ester may comprise 0.5% to 20% by weight, such as 0.5% to 15% by weight, such as 0.5% to 10% by weight, such as 0.5% to 8% by weight, such as 0.5% to 6% by weight, such as 0.5% by to 5% by weight, such as 0.5% to 4% by weight, such as 0.5% to 3% by weight, such as 0.5% to 2% by weight, such as 0.5% to 1.5% by weight, such as 0.5% to 1.0% by weight, such as 1% to 20% by weight, such as 1% to 15% by weight, such as 1% to 10% by weight, such as 1% to 8% by weight, such as 1% to 6% by weight, such as 1% by to 5% by weight, such as 1% to 4% by weight, such as 1% to 3% by weight, such as 1% to 2% by weight, such as 1% to 1.5% by weight, such as 1.5% to 20% by weight, such as 1.5% to 15% by weight, such as 1.5% to 10% by weight, such as 0.5% to
• the (meth)acrylic polymer may be derived from a reaction mixture comprising the hydroxyalkyl ester in an amount of 0.5% to 20% by weight, such as 0.5% to 15% by weight, such as 0.5% to 10% by weight, such as 0.5% to 8% by weight, such as 0.5% to 6% by weight, such as 0.5% by to 5% by weight, such as 0.5% to 4% by weight, such as 0.5% to 3% by weight, such as 0.5% to 2% by weight, such as 0.5% to 1.5% by weight, such as 0.5% to 1.0% by weight, such as 1% to 20% by weight, such as 1% to 15% by weight, such as 1% to 10% by weight, such as 1% to 8% by weight, such as 1% to 6% by weight, such as 1% by to 5% by weight, such as 1% to 4% by weight, such as 1% to 3% by weight, such as 1% to 2% by weight, such as 1% to 1.5% by weight, such as 1.5% to 20% by weight, such as 1.5% to 15% by weight,
• the inclusion of constitutional units comprising the residue of a hydroxyalkyl ester in the (meth)acrylic polymer results in a (meth)acrylic polymer comprising at least one hydroxyl group (although hydroxyl groups may be included by other methods).
• Hydroxyl groups resulting from inclusion of the hydroxyalkyl esters (or incorporated by other means) may react with a separately added crosslinking agent that comprises functional groups reactive with hydroxyl groups such as, for example, an aminoplast, phenolplast, polyepoxides and blocked polyisocyanates, or with N-alkoxymethyl amide groups or blocked isocyanato groups present in the (meth)acrylic polymer when self-crosslinking monomers that have groups that are reactive with the hydroxyl groups are incorporated into the (meth)acrylic polymer.
• the (meth)acrylic polymer may optionally comprise constitutional units comprising the residue of an alpha, beta-ethylenically unsaturated carboxylic acid.
• alpha, beta-ethylenically unsaturated carboxylic acids include those containing up to 10 carbon atoms such as acrylic acid and methacrylic acid.
• Non-limiting examples of other unsaturated acids are alpha, beta-ethylenically unsaturated dicarboxylic acids such as maleic acid or its anhydride, fumaric acid and itaconic acid. Also, the half esters of these dicarboxylic acids may be employed.
• constitutional units comprising the residue of the alpha, beta- ethylenically unsaturated carboxylic acids may comprise at least 0.5% by weight, such as at least 1% by weight, such as at least 1.5% by weight, based on the total weight of the (meth)acrylic polymer.
• the constitutional units comprising the residue of the alpha, beta- ethylenically unsaturated carboxylic acids may comprise no more than 10% by weight, such as no more than 8% by weight, such as no more than 6% by weight, such as no more than 5% by weight, such as no more than 4% by weight, such as no more than 3% by weight, such as no more than 2% by weight, such as no more than 1.5% by weight, such as no more than 1.0% by weight, based on the total weight of the (meth)acrylic polymer.
• the constitutional units comprising the residue of the alpha, beta-ethylenically unsaturated carboxylic acids may comprise 0.5% to 10% by weight, such as 0.5% to 8% by weight, such as 0.5% to 6% by weight, such as 0.5% by to 5% by weight, such as 0.5% to 4% by weight, such as 0.5% to 3% by weight, such as 0.5% to 2% by weight, such as 0.5% to 1.5% by weight, such as 0.5% to 1.0% by weight, such as 1% to 10% by weight, such as 1% to 8% by weight, such as 1% to 6% by weight, such as 1% by to 5% by weight, such as 1% to 4% by weight, such as 1% to 3% by weight, such as 1% to 2% by weight, such as 1% to 1.5% by weight, such as 1.5% to 10% by weight, such as 1.5% to 8% by weight, such as 1.5% to 6% by weight, such as 1.5% by to 5% by weight, such as 1.5% to 4% by weight, such as 1.5% to 3%
• the (me th) acrylic polymer may be derived from a reaction mixture comprising the alpha, beta-ethylenically unsaturated carboxylic acids in an amount of 0.5% to 10% by weight, such as 0.5% to 8% by weight, such as 0.5% to 6% by weight, such as 0.5% by to 5% by weight, such as 0.5% to 4% by weight, such as 0.5% to 3% by weight, such as 0.5% to 2% by weight, such as 0.5% to 1.5% by weight, such as 0.5% to 1.0% by weight, such as 1% to 10% by weight, such as 1% to 8% by weight, such as 1% to 6% by weight, such as 1% by to 5% by weight, such as 1% to 4% by weight, such as 1% to 3% by weight, such as 1% to 2% by weight, such as 1% to 1.5% by weight, such as 1.5% to 10% by weight, such as 1.5% to 8% by weight, such as 1.5% to 6% by weight, such as 1.5% by to 5% by weight, such as 1.
• the (meth)acrylic polymer may have a theoretical acid equivalent weight of at least 350 grams/equivalent, such as at least 878 grams/equivalent, such as at least 1,757 grams/equivalent, and may be no more than 17,570 grams/equivalent, such as no more than 12,000 grams/equivalent, such as no more than 7,000 grams/equivalent.
• the (meth)acrylic polymer may have a theoretical acid equivalent weight of 350 to 17,570 grams/equivalent, such as 878 to 12,000 grams/equivalent, such as 1,757 to 7,000 grams/equivalent.
• the (meth)acrylic polymer optionally may comprise constitutional units comprising the residue of an ethylenically unsaturated monomer comprising a heterocyclic group.
• ethylenically unsaturated monomers comprising a heterocyclic group include epoxy functional ethylenically unsaturated monomers, such as glycidyl (meth)acrylate, vinyl pyrrolidone and vinyl caprolactam, among others.
• the constitutional units comprising the residue of the ethylenically unsaturated monomers comprising a heterocyclic group may, if present, comprise at least 0.5% by weight, such as at least 1% by weight, such as at least 2% by weight, such as at least 3% by weight, such as at least 4% by weight, such as at least 5% by weight, such as at least 8% by weight, based on the total weight of the (meth)acrylic polymer.
• the constitutional units comprising the residue of the ethylenically unsaturated monomers comprising a heterocyclic group may, if present, comprise no more than 50% by weight, such as no more than 40% by weight, such as no more than 27% by weight, such as no more than 20% by weight, such as no more than 15% by weight, such as no more than 10% by weight, based on the total weight of the (meth)acrylic polymer.
• the constitutional units comprising the residue of the ethylenically unsaturated monomers comprising a heterocyclic group may comprise 0% to 50% by weight, such as 0.5% to 50% by weight, such as 0.5% to 40% by weight, such as 0.5% to 27% by weight, such as 0.5% to 20% by weight, such as 0.5% to 15% by weight, such as 0.5% to 10% by weight, such as 1% to 50% by weight, such as 1% to 40% by weight, such as 1% to 27% by weight, such as 1% to 20% by weight, such as 1% to 15% by weight, such as 1% to 10% by weight, such as 2% to 50% by weight, such as 2% to 40% by weight, such as 2% to 27% by weight, such as 2% to 20% by weight, such as 2% to 15% by weight, such as 2% to 10% by weight, such as 3% to 50% by weight, such as 3% to 40% by weight, such as 3% to 27% by weight, such as 3% to 20% by weight, such as 3% to 15% by weight, such as 2% to
• the (meth)acrylic polymer may be derived from a reaction mixture comprising the ethylenically unsaturated monomers comprising a heterocyclic group in an amount of such as 0.5% to 50% by weight, such as 0.5% to 40% by weight, such as 0.5% to 27% by weight, such as 0.5% to 20% by weight, such as 0.5% to 15% by weight, such as 0.5% to 10% by weight, such as 1% to 50% by weight, such as 1% to 40% by weight, such as 1% to 27% by weight, such as 1% to 20% by weight, such as 1% to 15% by weight, such as 1% to 10% by weight, such as 2% to 50% by weight, such as 2% to 40% by weight, such as 2% to 27% by weight, such as 2% to 20% by weight, such as 2% to 15% by weight, such as 2% to 10% by weight, such as 3% to 50% by weight, such as 3% to 40% by weight, such as 3% to 27% by weight, such as 2% to 20% by weight, such as 2% to 15% by
• the (meth)acrylic polymer may comprise constitutional units comprising the residue of a self-crosslinking monomer, and the (meth)acrylic polymer may comprise a self-crosslinking (meth)acrylic polymer.
• self-crosslinking monomer refers to monomers that incorporate functional groups that may react with other functional groups present on the (meth)acrylic polymer to a crosslink between the (meth)acrylic polymer or more than one (meth)acrylic polymer.
• Non-limiting examples of self-crosslinking monomers include N-alkoxymethyl (meth)acrylamide monomers such as N-butoxy methyl (meth) acrylamide and N-isopropoxymethyl (meth)acrylamide, as well as self-crosslinking monomers containing blocked isocyanate groups, such as isocyanatoethyl (meth)acrylate in which the isocyanato group is reacted ("blocked") with a compound that unblocks at curing temperature.
• suitable blocking agents include epsilon-caprolactone and methylethyl ketoxime.
• the constitutional units comprising the residue of the self-crosslinking monomer may comprise at least 0.5% by weight, such as at least 1% by weight, such as at least 1.5% by weight, based on the total weight of the (meth)acrylic polymer.
• the constitutional units comprising the residue of the self-crosslinking monomer may comprise no more than 20% by weight, such as no more than 15% by weight, such as no more than 8% by weight, such as no more than 6% by weight, such as no more than 5% by weight, such as no more than 4% by weight, such as no more than 3% by weight, such as no more than 2% by weight, such as no more than 1.5% by weight, such as no more than 1.0% by weight, based on the total weight of the (meth)acrylic polymer.
• the constitutional units comprising the residue of the self-crosslinking monomer may comprise 0.5% to 20% by weight, such as 0.5% to 15% by weight, such as 0.5% to 10% by weight, such as 0.5% to 8% by weight, such as 0.5% to 6% by weight, such as 0.5% by to 5% by weight, such as 0.5% to 4% by weight, such as 0.5% to 3% by weight, such as 0.5% to 2% by weight, such as 0.5% to 1.5% by weight, such as 0.5% to 1.0% by weight, such as 1% to 20% by weight, such as 1% to 15% by weight, such as 1% to 10% by weight, such as 1% to 8% by weight, such as 1% to 6% by weight, such as 1% by to 5% by weight, such as 1% to 4% by weight, such as 1% to 3% by weight, such as 1% to 2% by weight, such as 1% to 1.5% by weight, such as 1.5% to 20% by weight, such as 1.5% to 15% by weight, such as 1.5% to 10% by weight, such as 0.5% to
• the (meth)acrylic polymer may be derived from a reaction mixture comprising the self-crosslinking monomer in an amount of 0.5% to 20% by weight, such as 0.5% to 15% by weight, such as 0.5% to 10% by weight, such as 0.5% to 8% by weight, such as 0.5% to 6% by weight, such as 0.5% by to 5% by weight, such as 0.5% to 4% by weight, such as 0.5% to 3% by weight, such as 0.5% to 2% by weight, such as 0.5% to 1.5% by weight, such as 0.5% to 1.0% by weight, such as 1% to 20% by weight, such as 1% to 15% by weight, such as 1% to 10% by weight, such as 1% to 8% by weight, such as 1% to 6% by weight, such as 1% by to 5% by weight, such as 1% to 4% by weight, such as 1% to 3% by weight, such as 1% to 2% by weight, such as 1% to 1.5% by weight, such as 1.5% to 20% by weight, such as 1.5% to 15% by weight,
• the (meth)acrylic polymer may comprise constitutional units comprising the residue of other alpha, beta-ethylenically unsaturated monomers.
• other alpha, beta-ethylenically unsaturated monomers include vinyl aromatic compounds such as styrene, alpha-methyl styrene, alpha-chlorostyrene and vinyl toluene; organic nitriles such as acrylonitrile and methacrylonitrile; allyl monomers such as allyl chloride and allyl cyanide; monomeric dienes such as 1,3-butadiene and 2-methyl- 1,3-butadiene; and acetoacetoxyalkyl (meth)acrylates such as acetoacetoxyethyl methacrylate (AAEM) (which may be self crosslinking).
• AAEM acetoacetoxyethyl methacrylate
• the constitutional units comprising the residue of the other alpha, beta- ethylenically unsaturated monomers may comprise at least at least 0.5% by weight, such as at least 1% by weight, such as at least 1.5% by weight, based on the total weight of the (meth)acrylic polymer.
• the constitutional units comprising the residue of the other alpha, beta- ethylenically unsaturated monomers may comprise 20% by weight, such as no more than 15% by weight, such as no more than 8% by weight, such as no more than 6% by weight, such as no more than 5% by weight, such as no more than 4% by weight, such as no more than 3% by weight, such as no more than 2% by weight, such as no more than 1.5% by weight, such as no more than 1.0% by weight, based on the total weight of the (meth)acrylic polymer.
• the constitutional units comprising the residue of the other alpha, beta-ethylenically unsaturated monomers may comprise 0.5% to 20% by weight, such as 0.5% to 15% by weight, such as 0.5% to 10% by weight, such as 0.5% to 8% by weight, such as 0.5% to 6% by weight, such as 0.5% by to 5% by weight, such as 0.5% to 4% by weight, such as 0.5% to 3% by weight, such as 0.5% to 2% by weight, such as 0.5% to 1.5% by weight, such as 0.5% to 1.0% by weight, such as 1% to 20% by weight, such as 1% to 15% by weight, such as 1% to 10% by weight, such as 1% to 8% by weight, such as 1% to 6% by weight, such as 1% by to 5% by weight, such as 1% to 4% by weight, such as 1% to 3% by weight, such as 1% to 2% by weight, such as 1% to 1.5% by weight, such as 1.5% to 20% by weight, such as 1.5% to 15% by weight, such as 1.5%
• the (meth)acrylic polymer may be derived from a reaction mixture comprising the other alpha, beta-ethylenically unsaturated monomers in an amount of 0.5% to 20% by weight, such as 0.5% to 15% by weight, such as 0.5% to 10% by weight, such as 0.5% to 8% by weight, such as 0.5% to 6% by weight, such as 0.5% by to 5% by weight, such as 0.5% to 4% by weight, such as 0.5% to 3% by weight, such as 0.5% to 2% by weight, such as 0.5% to 1.5% by weight, such as 0.5% to 1.0% by weight, such as 1% to 20% by weight, such as 1% to 15% by weight, such as 1% to 10% by weight, such as 1% to 8% by weight, such as 1% to 6% by weight, such as 1% by to 5% by weight, such as 1% to 4% by weight, such as 1% to 3% by weight, such as 1% to 2% by weight, such as 1% to 1.5% by weight, such as 1.5% to 20% by weight
• the monomers and relative amounts may be selected such that the resulting
• the (meth)acrylic polymer has a Tg of 100°C or less.
• the resulting (meth)acrylic polymer may have a Tg of, for example, at least -50°C, such as at least -40°C, such as -30°C, such as, -20°C, such as -15°C, such as -10°C, such as -5°C, such as 0°C.
• the resulting (meth)acrylic polymer may have a Tg of, for example, no more than +70°C, such as no more than +60°C, such as no more than +50°C, such as no more than +40°C, such as no more than +25°C, such as no more than +15°C, such as no more than +10°C, such as no more than +5°C, such as no more than 0°C.
• the resulting (meth)acrylic polymer may have a Tg of, for example, -50 to +70°C, such as -50 to +60°C, such as -50 to +50°C, such as -50 to +40°C, such as -50 to +25°C, such as -50 to +20°C, such as -50 to +15°C, such as -50 to +10°C, such as -50 to +5°C, such as -50 to 0°C, such as -40 to +50°C, such as -40 to +40°C, such as -40 to +25°C, such as -40 to +20°C, such as -40 to +15°C, such as -40 to +10°C, such as -40 to +5°C, such as -40 to 0°C, such as -30 to +50°C, such as -30 to +40°C, such as -30 to +25°C, such as -30 to +20°C, such as -30 to +15°C, such as -30
• the (meth)acrylic polymer may have a number average molecular weight of at least 2,500 g/mol, such as at least 5,000 g/mol, such as at least 7,500 g/mol, such at least 10,000 g/mol.
• the (meth)acrylic polymer may have a number average molecular weight of no more than 100,000 g/mol, such as no more than 75,000 g/mol, such as no more than 50,000 g/mol, such as no more than 25,000 g/mol, such as no more than 20,000 g/mol, such as no more than 15,000 g/mol, such as no more than 10,000 g/mol, such as no more than 7,500 g/mol.
• the (meth)acrylic polymer may have a number average molecular weight of 2,500 to 100,000 g/mol, such as 2,500 to 75,000 g/mol, such as 2,500 to 50,000 g/mol, such as 2,500 to 25,000 g/mol, such as 2,500 to 20,000 g/mol, such as 2,500 to 15,000 g/mol, such as 2,500 to 12,500 g/mol, such as 2,500 to 10,000 g/mol, such as 2,500 to 7,500 g/mol, 5,000 to 100,000 g/mol, such as
• 5,000 to 75,000 g/mol such as 5,000 to 50,000 g/mol, such as 5,000 to 25,000 g/mol, such as 5,000 to 20,000 g/mol, such as 5,000 to 15,000 g/mol, such as 5,000 to 12,500 g/mol, such as 5,000 to 10,000 g/mol, such as 5,000 to 7,500 g/mol, 7,500 to 100,000 g/mol, such as 7,500 to 75,000 g/mol, such as 7,500 to 50,000 g/mol, such as 7,500 to 25,000 g/mol, such as 7,500 to 20,000 g/mol, such as 7,500 to 15,000 g/mol, such as 7,500 to 12,500 g/mol, such as 7,500 to 10,000 g/mol, 10,000 to 100,000 g/mol, such as 10,000 to 75,000 g/mol, such as 10,000 to 50,000 g/mol, such as 10,000 to 25,000 g/mol, such as 10,000 to 20,000 g/mol, such as 10,000 to 15,000 g/mol, such as 10,000 to 12,500
• the (meth)acrylic polymer may have a weight average molecular weight of at least at least 5,000 g/mol, such as at least 10,000 g/mol, such as at least 15,000 g/mol, such at least 20,000 g/mol.
• the (meth)acrylic polymer may have a weight average molecular weight of no more than 200,000 g/mol, such as no more than 150,000 g/mol, such as no more than 100,000 g/mol, such as no more than 50,000 g/mol, such as no more than 40,000 g/mol, such as no more than 30,000 g/mol, such as no more than 20,000 g/mol, such as no more than 15,000 g/mol.
• the (meth)acrylic polymer may have a weight average molecular weight of 5,000 to 200,000 g/mol, such as 5,000 to 150,000 g/mol, such as 5,000 to 100,000 g/mol, such as 5,000 to 50,000 g/mol, such as 5,000 to 40,000 g/mol, such as 5,000 to 30,000 g/mol, such as 5,000 to 25,000 g/mol, such as 5,000 to 20,000 g/mol, such as 5,000 to 15,000 g/mol, 10,000 to 200,000 g/mol, such as 10,000 to 150,000 g/mol, such as 10,000 to 100,000 g/mol, such as 10,000 to 50,000 g/mol, such as 10,000 to 40,000 g/mol, such as 10,000 to 30,000 g/mol, such as 10,000 to 25,000 g/mol, such as 10,000 to 20,000 g/mol, such as 10,000 to 15,000 g/mol, 15,000 to 200,000 g/mol, such as 15,000 to 100,000 g/mol, such as 15,000 to 100,000 g/mol, such
• the (meth)acrylic polymer s may be prepared by conventional free radical initiated solution polymerization techniques in which the polymerizable monomers are dissolved in an organic medium comprising a solvent or a mixture of solvents and polymerized in the presence of a free radical initiator until conversion is complete.
• Examples of free radical initiators are those which are soluble in the mixture of monomers such as azobisisobutyronitrile, azobis(alpha, gamma- methylvaleronitrile), tertiary- butyl perbenzoate, tertiary-butyl peracetate, benzoyl peroxide, ditertiary-butyl peroxide and tertiary amyl peroxy 2-ethylhexyl carbonate.
• monomers such as azobisisobutyronitrile, azobis(alpha, gamma- methylvaleronitrile), tertiary- butyl perbenzoate, tertiary-butyl peracetate, benzoyl peroxide, ditertiary-butyl peroxide and tertiary amyl peroxy 2-ethylhexyl carbonate.
• a chain transfer agent which is soluble in the mixture of monomers such as alkyl mercaptans, for example, tertiary-dodecyl mercaptan; ketones such as methyl ethyl ketone, chlorohydrocarbons such as chloroform can be used.
• a chain transfer agent provides control over the molecular weight to give products having required viscosity for various coating applications.
• Tertiary-dodecyl mercaptan is preferred because it results in high conversion of monomer to polymeric product.
• the solvent may be first heated to reflux and the mixture of polymerizable monomers containing the free radical initiator may be added slowly to the refluxing solvent.
• the reaction mixture is then held at polymerizing temperatures so as to reduce the free monomer content, such as to below 1.0 percent and usually below 0.5 percent, based on the total weight of the mixture of polymerizable monomers.
• the (meth)acrylic polymers prepared as described above may have a weight average molecular weight of about 5,000 to 500,000 g/mol, such as 10,000 to 100,000 g/mol, and 25,000 to 50,000 g/mol.
• the (meth)acrylic polymer may be present in the binder in amounts of at least 1% by weight, such as at least 2% by weight, such as at least 3% by weight, such as at least 4% by weight, such as at least 5% by weight, based on the total weight of the binder solids.
• the (meth)acrylic polymer may be present in the binder in amounts of no more than 20% by weight, such as no more than 15% by weight, such as no more than 12.5% by weight, such as no more than 10% by weight, such as no more than 5% by weight, based on the total weight of the binder solids.
• the (meth)acrylic polymer may be present in the binder in amounts of 1% to 20% by weight, such as 1% to 15% by weight, such as 1% to 12.5% by weight, such as 1% to 10% by weight, such as 1% to 5% by weight, such as 2% to 20% by weight, such as 2% to 15% by weight, such as 2% to 12.5% by weight, such as 2% to 10% by weight, such as 2% to 5% by weight, such as 3% to 20% by weight, such as 3% to 15% by weight, such as 3% to 12.5% by weight, such as 3% to 10% by weight, such as 3% to 5% by weight, such as 4% to 20% by weight, such as 4% to 15% by weight, such as 4% to 12.5% by weight, such as 4% to 10% by weight, such as 4% to 5% by weight, such as 5% to 20% by weight, such as 5% to 15% by weight, such as 5% to 12.5% by weight, such as 5% to 10% by weight, based on the total weight of the binder solids
• the binder composition and/or slurry composition further comprises an organic medium comprising, consisting essentially of, or consisting of a trialkyl phosphate solvent.
• organic medium refers to a liquid medium comprising less than 50% by weight water, based on the total weight of the organic medium.
• Such organic mediums may comprise less than 45% by weight water, such as less than 40% by weight water, such as less than 45% by weight water, such as less than 30% by weight water, such as less than 25% by weight water, such as less than 20% by weight water, such as less than 15% by weigh water, such as less than 10% by weight water, such as less than 5% by weight water, such as less than 2.5% by weight water, such as less than 1% by weight water, such as less than 0.1% by weight water, based on the total weight of the organic medium.
• the organic medium may be free of water, i.e., 0.00% by weight water.
• Organic solvent(s) comprise more than 50 % by weight of the organic medium, such as at least 70% by weight, such as at least 80% by weight, such as at least 90% by weight, such as at least 95% by weight, such as at least 99% by weight, such as at least 99.9% by weight, such as 100% by weight, based on the total weight of the organic medium.
• the organic solvent(s) may comprise 50.1% to 100% by weight, such as 70% to 100% by weight, such as 80% to 100% by weight, such as 90% to 100% by weight, such as 95% to 100% by weight, such as 99% to 100% by weight, such as 99.9% to 100% by weight, based on the total weight of the organic medium.
• the trialkyl phosphate may comprise, for example, trimethylphosphate, triethylphosphate, tripropylphosphate, tributylphosphate, or the like, or combinations thereof.
• the organic medium may optionally comprise a co-solvent.
• the co-solvent may comprise butyl pyrrolidone, 1,2,3-triacetoxypropane, 3-methoxy-N,N-dimethylpropanamide, ethyl acetoacetate, gamma-butyrolactone, propylene glycol methyl ether, cyclohexanone, propylene carbonate, dimethyl adipate, propylene glycol methyl ether acetate, dibasic ester (DBE), dibasic ester 5 (DBE-5), 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), propylene glycol diacetate, dimethyl phthalate, methyl isoamyl ketone, ethyl propionate, l-ethoxy-2- propanol, dipropylene glycol dimethyl ether, saturated and unsaturated linear and cyclic ketones (commercially available as a mixture thereof as EastmanTM C-l 1 Ketone from Eastman Chemical Company), diisobutyl ketone
• the fluoropolymer of the binder compositions and/or slurry composition may be solubilized or solved in the trialkyl phosphate solvent at room temperature, i.e., about 23°C, and pressure.
• the organic medium may be present in an amount of at least 10% by weight, such as at least 15% by weight, such as at least 20% by weight, such as at least 30% by weight, such as at least 35% by weight, such as at least 40% by weight, and may be present in an amount of no more than 80% by weight, such as no more than 70% by weight, such as no more than 60% by weight, such as no more than 50% by weight, such as no more than 45% by weight, such as no more than 45% by weight, such as no more than 40% by weight, such as no more than 35% by weight, such as no more than 29% by weight, such as no more than 25% by weight, based on the total weight of the binder composition and/or slurry composition.
• the organic medium may be present in an amount of such as 20% to 80% by weight, 10% to 70% by weight, such as 30% to 70% by weight, such as 35% to 60% by weight, such as 40% to 50% by weight, 15% to 60% by weight, 15% to 50% by weight, 15% to 45% by weight, 15% to 40% by weight, 15% to 35% by weight, 15% to 29% by weight, 15% to 25% by weight, based on the total weight of the binder composition and/or slurry composition.
• the binder composition and/or slurry composition may be substantially free, essentially free, or completely free of N-Methyl-2-pyrrolidone (NMP).
• the binder composition and/or slurry composition is “substantially free” of NMP if NMP is present, if at all, in an amount of less than 5% by weight, based on the total weight of the binder composition and/or slurry composition.
• the binder composition and/or slurry composition is “essentially free” of NMP if NMP is present, if at all, in an amount of less than 0.3% by weight, based on the total weight of the binder composition and/or slurry composition.
• the slurry composition is “completely free” of NMP if NMP is not present in the binder composition and/or slurry composition, i.e., 0.000% by weight, based on the total weight of the binder composition and/or slurry composition.
• the binder composition and/or slurry composition may be substantially free, essentially free, or completely free of ketones such as methyl ethyl ketone, cyclohexanone, isophorone, acetophenone.
• the binder composition and/or slurry composition may be substantially free, essentially free, or completely free of ethers such as the Ci to C4 alkyl ethers of ethylene or propylene glycol.
• the fluoropolymer, binder composition and/or slurry composition may be substantially free, essentially free, or completely free of fluoroethylene, such as tetrafluoroethy lene .
• the fluoropolymer, binder composition and/or slurry composition may be substantially free, essentially free, or completely free of fluorosurfactant.
• the binder composition and/or slurry composition may be substantially free, essentially free, or completely free of siloxane.
• the binder composition and/or slurry composition may optionally further comprise a separately added crosslinking agent for reaction with the (meth)acrylic polymer.
• the crosslinking agent should be soluble or dispersible in the organic medium and be reactive with active hydrogen groups of the (meth)acrylic polymer, such as the carboxylic acid groups and the hydroxyl groups, if present.
• suitable crosslinking agents include aminoplast resins, blocked polyisocyanates and poly epoxides.
• aminoplast resins for use as a crossslinking agent are those which are formed by reacting a triazine such as melamine or benzoguanamine with formaldehyde. These reaction products contain reactive N-methylol groups. Usually, these reactive groups are etherified with methanol, ethanol, butanol including mixtures thereof to moderate their reactivity.
• Blocked polyisocyanate crosslinking agents are typically diisocyanates such as toluene diisocyanate, 1,6-hexamethylene diisocyanate and isophorone diisocyanate including isocyanato dimers and trimers thereof in which the isocyanate groups are reacted ("blocked") with a material such as epsilon-caprolactone and methylethyl ketoxime.
• the blocking agents unblock exposing isocyanate functionality that is reactive with the hydroxyl functionality associated with the (meth)acrylic polymer.
• Blocked polyisocyanate crosslinking agents are commercially available from Covestro as DESMODUR BL.
• Carbodiimide crosslinking agents may be in monomeric or polymeric form, or a mixture thereof.
• Carbodiimide crosslinking agents refer to compounds having the following structure:
• R and R’ may each individually comprise an aliphatic, aromatic, alkylaromatic, carboxylic, or heterocyclic group.
• R and R’ may each individually comprise an aliphatic, aromatic, alkylaromatic, carboxylic, or heterocyclic group.
• carbodiimide crosslinking agents include, for example, those sold under the trade name CARBODILITE available from Nisshinbo Chemical Inc., such as CARBODILITE V-02-L2, CARBODILITE SV-02, CARBODILITE E-02, CARBODILITE SW-12G, CARBODILITE V-10 and CARBODILITE E-05.
• polyepoxide crosslinking agents are epoxy-containing (meth)acrylic polymers such as those prepared from glycidyl methacrylate copolymerized with other vinyl monomers, polyglycidyl ethers of polyhydric phenols such as the diglycidyl ether of bisphenol A; and cycloaliphatic polyepoxides such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate and bis(3,4-epoxy-6-methylcyclohexyl-methyl) adipate.
• epoxy-containing (meth)acrylic polymers such as those prepared from glycidyl methacrylate copolymerized with other vinyl monomers, polyglycidyl ethers of polyhydric phenols such as the diglycidyl ether of bisphenol A; and cycloaliphatic polyepoxides such as 3,4-epoxycyclohexylmethyl-3,4-epoxycycl
• the crosslinking agents include those associated with crosslinking monomers and separately added crosslinking agents, react with the hydrophilic groups, such as active hydrogen functional groups of the (meth)acrylic polymer preventing these groups from absorbing moisture that could be problematic in a lithium ion battery.
• the separately added crosslinker may be present in the binder in amounts of up to
• the % by weight being based on the total weight of the binder solids.
• the binder composition and/or slurry composition may optionally further comprise an adhesion promoter.
• the adhesion promoter may comprise a portion or all of the fluoropolymer of the binder composition and/or slurry composition.
• the adhesion promoter may comprise a polyvinylidene fluoride copolymer different than the fluoropolymer described above, or a thermoplastic material.
• the polyvinylidene fluoride copolymer adhesion promoter comprises constitutional units comprising the residue of vinylidene fluoride and at least one of (i) a (meth)acrylic acid; and/or (ii) a hydroxyalkyl (meth)acrylate.
• the (meth)acrylic acid may comprise acrylic acid, methacrylic acid, or combinations thereof.
• the hydroxyalkyl (meth) acrylate may comprise a Ci to Cs hydroxyalkyl (meth)acrylate, such as, for example, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, or combinations thereof.
• a commercially available example of such an addition polymer includes SOLEF 5130, available from Solvay.
• the polyvinylidene fluoride copolymer may be dispersed or solubilized in the organic medium of the binder composition and/or slurry composition.
• the polyvinylidene fluoride copolymer adhesion promoter may have a weight average molecular weight as described above with respect to the fluoropolymer.
• the adhesion promoter may be present in the binder composition and/or slurry composition in an amount of up to 100% by weight, such as 10% to 60% by weight, 20% to 60% by weight, such as 30% to 60% by weight, such as 10% to 50% by weight, such as 15% to 40% by weight, such as 20% to 30% by weight, such as 30% to 35% by weight, based on the total weight of the binder solids.
• the coating film produced from the binder composition and/or slurry composition comprising an adhesion promoter may possess improved adhesion to the current collector compared to a coating film produced from a binder composition and/or slurry composition that does not include the adhesion promoter.
• the use of the coating film resulting from the binder composition and/or slurry composition comprising an adhesion promoter may improve adhesion by at least 50%, such as at least 100%, such as at least 200%, such as at least 300%, such as at least 400%, compared to a coating film produced from a binder composition and/or slurry composition that does not include the adhesion promoter.
• the binder composition may have a resin solids content of from 30% to 80% by weight, such as 40% to 70% by weight, based on the total weight of the binder composition.
• resin solids may be used synonymously with “binder solids” and include the fluoropolymer, (meth)acrylic polymer, and, if present, adhesion promoter, and separately added crosslinking agent.
• binder composition refers to a dispersion of the binder solids in the organic medium.
• the fluoropolymer may be present in the binder composition and/or slurry composition in amounts of 40% to 96% by weight, such as 50% to 90% by weight; the (meth)acrylic polymer may be present in amounts of 2% to 20% by weight, such as 5% to 15% by weight; the adhesion promoter may be present in the binder composition and/or slurry composition in an amount of 10% to 60% by weight, 20% to 60% by weight, such as 30% to 60% by weight, such as 10% to 50% by weight, such as 15% to 40% by weight, such as 20% to 30% by weight, such as 35% to 35% by weight; and the separately added crosslinker may be present in amounts of up to 15% by weight, such as 1% to 15% by weight, the % by weight being based on the total weight of the binder solids.
• the organic medium is present in the binder composition and/or slurry composition in amounts of 10% to 70% by weight, such as 10% to 65% by weight, such as 15% to 60% by weight, such as 15% to 40% by weight, such as 30% to 60% by weight, based on total weight of the binder composition and/or slurry composition.
• the binder solids may be present in the slurry composition in amounts of at least
• 0.1% by weight such as at least 0.5% by weight, such as at least 1% by weight, such as at least 1.5% by weight, such as at least 2% by weight, based on the total solids weight of the slurry.
• the binder solids may be present in the slurry composition in amounts of no more than 20% by weight, such as no more than 15% by weight, such as no more than 10% by weight, such as no more than 7.5% by weight, such as no more than 5% by weight, such as no more than 4% by weight, such as no more than 3% by weight, based on the total solids weight of the slurry.
• the binder solids may be present in the slurry composition in amounts of 0.1% to 20% by weight, such as 0.1% to 15% by weight, such as 0.1% to 10% by weight, such as 0.1% to 7.5% by weight, such as 0.1% to 5% by weight, such as 0.1% to 4% by weight, such as 0.1% to 3% by weight, such as 0.5% to 20% by weight, such as 0.5% to 15% by weight, such as 0.5% to 10% by weight, such as 0.5% to 7.5% by weight, such as 0.5% to 5% by weight, such as 0.5% to 4% by weight, such as 0.5% to 3% by weight, such as 1% to 20% by weight, such as 1% to 15% by weight, such as 1% to 10% by weight, such as 1% to 7.5% by weight, such as 1% to 5% by weight, such as 1% to 4% by weight, such as 1% to 3% by weight, such as 1.5% to 20% by weight, such as 1.5% to 15% by weight, such as 1.5% to 10% by weight, such as 1.5% to 7.5% by weight, such
• the fluoropolymer may be present in the slurry composition in an amount of
• 0.1% to 10% by weight such as 1% to 6% by weight, such as 1.3% to 4.5% by weight, such as 1.9% to 2.9% by weight, based on the total solids weight of the slurry composition.
• the (meth)acrylic polymer may be present in the slurry composition in an amount of 0.1% to 10% by weight, such as 1% to 6% by weight, such as 1.3% to 4.5% by weight, such as 1.9% to 2.9% by weight, based on the total solids weight of the slurry composition.
• the separately added crosslinking agent may be present in the slurry composition in an amount of 0.001% to 5% by weight, such as 0.002% to 2% by weight, such as 0.002 to 1% by weight, such as 0.005 to 0.5% by weight, such as 0.005 to 0.3% by weight, such as 0.1% to 5% by weight, based on the total solids weight of the slurry composition.
• the present disclosure is also directed to a slurry composition comprising the binder composition described above.
• the slurry composition may optionally further comprise an electrochemically active material.
• the material constituting the electrochemically active material contained in the slurry is not particularly limited and a suitable material can be selected according to the type of an electrical storage device of interest.
• the electrochemically active material may comprise a material for use as an active material for a positive electrode.
• the electrochemically active material may comprise a material capable of incorporating lithium (including incorporation through lithium intercalation/deintercalation), a material capable of lithium conversion, or combinations thereof.
• Non-limiting examples of electrochemicahy active materials capable of incorporating lithium include LiCoC , LiNiC , LiFePCU, LiCoPCU, LiMnC , LiMmCri, Li(NiMnCo)02,
• Li(NiCoAl)0 2 carbon-coated LiFePCU, and combinations thereof.
• materials capable of lithium conversion include sulfur, LiC , FeF2 and FeF3, Si, aluminum, tin, SnCo, Fe 3 0 4 , and combinations thereof.
• the electrochemicahy active material may comprise a material for use as an active material for a negative electrode.
• the electrochemicahy active material may comprise graphite, lithium titanate, silicon compounds, tin, tin compounds, sulfur, sulfur compounds, or a combination thereof.
• the electrochemicahy active material may be present in the slurry in amounts of
• 45% to 99% by weight such as 50% to 99% by weight, such as 55% to 99% by weight, such as
• 94% to 98% by weight such as 95% to 98% by weight, such as 96% to 98% by weight, such as
• the slurry composition may optionally further comprise an electrically conductive agent.
• electrically conductive agents include carbonaceous materials such as, activated carbon, carbon black such as acetylene black and furnace black, graphite, graphene, carbon nanotubes, carbon fibers, fullerene, and combinations thereof.
• the electrically conductive agent may be present in the slurry in amounts of at least 0.1% by weight, such as at least 0.5% by weight, such as at least 1% by weight, such as at least 1.5% by weight, such as at least 2% by weight, based on the total solids weight of the slurry.
• the electrically conductive agent may be present in the slurry in amounts of no more than 20% by weight, such as no more than 15% by weight, such as no more than 10% by weight, such as no more than 7.5% by weight, such as no more than 5% by weight, such as no more than 4% by weight, such as no more than 3% by weight, such as no more than 2.5% by weight, based on the total solids weight of the slurry.
• the electrically conductive agent may be present in the slurry in amounts of 0.1% to 20% by weight, such as 0.1% to 15% by weight, such as 0.1% to 10% by weight, such as 0.1% to 7.5% by weight, such as 0.1% to 5% by weight, such as 0.1% to 4% by weight, such as 0.1% to 3% by weight, such as 0.1% to 2.5% by weight, such as 0.5% to 20% by weight, such as 0.5% to 15% by weight, such as 0.5% to 10% by weight, such as 0.5% to 7.5% by weight, such as 0.5% to 5% by weight, such as 0.5% to 4% by weight, such as 0.5% to 3% by weight, such as 0.5% to 2.5% by weight, such as 1% to 20% by weight, such as 1% to 15% by weight, such as 1% to 10% by weight, such as 1% to 7.5% by weight, such as 1% to 5% by weight, such as 0.5% to 4% by weight, such as 0.5% to 3% by weight, such as 0.5% to 2.5% by weight, such as 1% to 20% by weight
• the slurry composition may be in the form of an electrode slurry composition comprising the binder, electrochemically active material and electrically conductive material, each as described above.
• the electrode slurry may comprise such materials present in the slurry composition in the amounts described above.
• the electrode slurry composition may comprise the electrochemically active material present in amounts of 45% to 95% by weight, such as 70% to 98% by weight; the binder solids from the binder composition present in amounts of 1% to 20% by weight, such as 1% to 10% by weight, such as 5% to 10% percent by weight; and the electrically conductive agent present in amounts of 1% to 20% by weight, such as 5% to 10% by weight, the percentages by weight based on the total solids weight of the electrode slurry composition.
• the electrode slurry composition comprising the organic medium, electrochemically active material, electrically conductive material, binder dispersion (which may include a separately added crosslinking agent), additional organic medium, if needed, and optional ingredients, may be prepared by combining the ingredients to form the slurry. These substances can be mixed together by agitation with a known means such as a stirrer, bead mill or high-pressure homogenizer.
• a mixer capable of stirring these components to such an extent that satisfactory dispersion conditions are met should be selected.
• the degree of dispersion can be measured with a particle gauge and mixing and dispersion are preferably carried out to ensure that agglomerates of 100 microns or more are not present.
• the mixers which meets this condition include ball mill, sand mill, pigment disperser, grinding machine, extruder, rotor stator, pug mill, ultrasonic disperser, homogenizer, planetary mixer, Hobart mixer, and combinations thereof.
• the slurry composition may have a solids content of at least 30% by weight, such as at least 40% by weight, such as at least 50% by weight, such as at least 55%, such as at least 60%, such as at least 65%, such as at least 71%, such as at least 75%, and may be no more than 90% by weight, such as no more than 85% by weight, such as no more than 75% by weight, the % by weight based on the total weight of the slurry composition.
• the slurry composition may have a solids content of 30% to 90% by weight, such as 40% to 85% by weight, such as 50% to 85% by weight, such as 55% to 85% by weight, such as 60% to 85% by weight, such as 65% to 85% by weight, such as 71% to 85% by weight, such as 75% to 85% by weight, based on the total weight of the slurry composition.
• the present disclosure is also directed to an electrode comprising an electrical current collector and a film on the electrical current collector, wherein the film comprises: (1) an electrochemically active material; and (2) a binder comprising: (a) at least one fluoropolymer comprising the residue of vinylidene fluoride; and (b) one or more (meth)acrylic polymers comprising constitutional units comprising the residue of: (i) 40% to 80% by weight of an alkyl ester of (meth)acrylic acid containing from 1 to 3 carbon atoms in the alkyl group; (ii) 18% to 48% by weight of an alkyl ester of (meth)acrylic acid containing from 4 to 18 carbon atoms in the alkyl group; (iii) 0.1% to 10% by weight of a hydroxyalkyl ester; (iv) 0% to 10% by weight of an alpha, beta-ethylenically unsaturated carboxylic acid; and (v) 0% to 20% by weight of an ethy
• the film may be deposited from the electrode slurry composition described above.
• the electrode may be a positive electrode or a negative electrode and may be manufactured by applying the above- described slurry composition to the surface of the current collector to form a coating film, and subsequently drying and/or curing the coating film.
• the coating film may have a thickness of at least 1 micron, such as 1 to 500 microns (pm), such as 1 to 150 pm, such as 25 to 150 pm, such as 30 to 125 pm.
• the coating film may comprise a cross-linked coating, and the film may further comprise the residue of a crosslinking agent.
• the current collector may comprise a conductive material, and the conductive material may comprise a metal such as iron, copper, aluminum, nickel, and alloys thereof, as well as stainless steel.
• the current collector may comprise aluminum or copper in the form of a mesh, sheet or foil.
• the shape and thickness of the current collector are not particularly limited, the current collector may have a thickness of about 0.001 to 0.5 mm, such as a mesh, sheet or foil having a thickness of about 0.001 to 0.5 mm.
• the current collector may be pretreated with a pretreatment composition prior to depositing the slurry composition.
• pretreatment composition refers to a composition that upon contact with the current collector, reacts with and chemically alters the current collector surface and binds to it to form a protective layer.
• the pretreatment composition may be a pretreatment composition comprising a group MB and/or IVB metal.
• group IIIB and/or IVB metal refers to an element that is in group MB or group IVB of the CAS Periodic Table of the Elements as is shown, for example, in the Handbook of Chemistry and Physics, 63 rd edition (1983).
• group MB and/or IVB metal compound refers to compounds that include at least one element that is in group MB or group IVB of the CAS Periodic Table of the Elements.
• Suitable pretreatment compositions and methods for pretreating the current collector are described in U.S. Patent No. 9,273,399 at col. 4, line 60 to col. 10, line 26, the cited portion of which is incorporated herein by reference.
• the pretreatment composition may be used to treat current collectors used to produce positive electrodes or negative electrodes.
• the method of applying the slurry composition to the current collector is not particularly limited.
• the slurry composition may be applied by doctor blade coating, dip coating, reverse roll coating, direct roll coating, gravure coating, extrusion coating, immersion or brushing.
• the application quantity of the slurry composition is not particularly limited, the thickness of the coating formed after the organic medium is removed may be 25 to 150 microns (pm), such as 30 to 125 pm.
• Drying and/or crosslinking the coating film after application can be done, for example, by heating at elevated temperature, such as at least 50°C, such as at least 60°C, such as 50-145°C, such as 60-120°C, such as 65-110°C.
• elevated temperature such as at least 50°C, such as at least 60°C, such as 50-145°C, such as 60-120°C, such as 65-110°C.
• the time of heating will depend somewhat on the temperature. Generally, higher temperatures require less time for curing. Typically, curing times are for at least 5 minutes, such as 5 to 60 minutes.
• the temperature and time should be sufficient such that the (meth)acrylic polymer in the cured film is crosslinked (if applicable), that is, covalent bonds are formed between co-reactive groups on the (meth)acrylic polymer polymer chain, such as carboxylic acid groups and hydroxyl groups and the N-methylol and/or the N-methylol ether groups of an aminoplast, isocyanato groups of a blocked polyisocyanate crosslinking agent, or in the case of a self-curing (meth)acrylic polymer, the N- alkoxymethyl amide groups or blocked isocyanato groups.
• the extent of cure or crosslinking may be measured as resistance to solvents such as methyl ethyl ketone (MEK).
• the test is performed as described in ASTM D-540293. The number of double mbs, one back and forth motion, is reported. This test is often referred to as "MEK Resistance". Accordingly, the (meth)acrylic polymer and crosslinking agent (inclusive of self-curing (meth)acrylic polymers and (meth)acrylic polymers with separately added crosslinking agents) is isolated from the binder composition, deposited as a film and heated for the temperature and time that the binder film is heated. The film is then measured for MEK Resistance with the number of double rubs reported. Accordingly, a crosslinked (meth)acrylic polymer will have an MEK Resistance of at least 50 double mbs, such as at least 75 double mbs.
• the crosslinked (meth)acrylic polymer may be substantially solvent resistant to the solvents of the electrolyte mentioned below.
• Other methods of drying the coating film include ambient temperature drying, microwave drying and infrared drying, and other methods of curing the coating film include e-beam curing and UV curing.
• lithium ions may be released from the negative electrode and carry the current to the positive electrode. This process may include the process known as deintercalation.
• the lithium ions migrate from the electrochemically active material in the positive electrode to the negative electrode where they become embedded in the electrochemically active material present in the negative electrode. This process may include the process known as intercalation.
• the present disclosure is also directed to an electrical storage device.
• An electrical storage device can be manufactured by using the above electrodes prepared from the electrode slurry composition of the present disclosure.
• the electrical storage device comprises an electrode, a counter electrode and an electrolyte.
• the electrode, counter-electrode or both may comprise the electrode of the present disclosure, as long as one electrode is a positive electrode, and one electrode is a negative electrode.
• Electrical storage devices include, but are not limited to, a cell, a battery, a battery pack, a secondary battery, a capacitor, and a supercapacitor.
• the electrical storage device includes an electrolytic solution and can be manufactured by using parts such as a separator in accordance with a commonly used method.
• a negative electrode and a positive electrode are assembled together with a separator there between, the resulting assembly is rolled or bent in accordance with the shape of a battery and put into a battery container, an electrolytic solution is injected into the battery container, and the battery container is sealed up.
• the shape of the battery may be like a coin, button or sheet, cylindrical, square or flat.
• the electrolytic solution may be liquid or gel, and an electrolytic solution which can serve effectively as a battery may be selected from among known electrolytic solutions which are used in electrical storage devices in accordance with the types of a negative electrode active material and a positive electrode active material.
• the electrolytic solution may be a solution containing an electrolyte dissolved in a suitable solvent.
• the electrolyte may be conventionally known lithium salt for lithium ion secondary batteries.
• lithium salt examples include LiCICU, LiBF4, LiPF6, LiCF 3 C0 2 , LiAsF6, LiSbF6, LiBioClio, LiAlCU, LiCl, LiBr, LiB(C 2 H 5 )4, LiB(C 6 H 5 )4, LiCFvSC LiCH S0 3 , LiC 4 F 9 S0 3 , Li(CF S0 2 )2N, LiB 4 CH S0 3 Li and CF 3 SO 3 LL
• the solvent for dissolving the above electrolyte is not particularly limited and examples thereof include carbonate compounds such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate; lactone compounds such as g-butyl lactone; ether compounds such as trimethoxymethane, 1,2- dimethoxyethane, diethyl ether, 2-ethoxyethane, tetrahydrofuran and 2-methyltetrahydro
• polymer refers broadly to oligomers and both homopolymers and copolymers.
• resin is used interchangeably with “polymer”.
• the terms "acrylic” and “acrylate” are used interchangeably (unless to do so would alter the intended meaning) and include acrylic acids, anhydrides, and derivatives thereof, such as their C1-C5 alkyl esters, lower alkyl-substituted acrylic acids, e.g., C1-C2 substituted acrylic acids, such as methacrylic acid, 2-ethylacrylic acid, etc., and their C1-C4 alkyl esters, unless clearly indicated otherwise.
• the terms “ (me th) acrylic” or “(meth)acrylate” are intended to cover both the acrylic/acrylate and methacrylic/methacrylate forms of the indicated material, e.g., a (meth)acrylate monomer.
• (meth) acrylic polymer refers to polymers prepared from one or more (meth) acrylic monomers.
• molecular weights are determined by gel permeation chromatography using a polystyrene standard. Unless otherwise indicated molecular weights are on a weight average basis.
• weight average molecular weight or “(Mw)” means the weight average molecular weight (M w ) as determined by gel permeation chromatography using a polystyrene standard according to ASTM D6579-11 (“Standard Practice for Molecular Weight Averages and Molecular Weight Distribution of Hydrocarbon, Rosin and Terpene Resins by Size Exclusion Chromatography”. UV detector; 254nm, solvent: unstabilised THF, retention time marker: toluene, sample concentration: 2mg/ml).
• the term “number average molecular weight” or “(M n )” means the number average molecular weight (M n ) as determined by gel permeation chromatography using a polystyrene standard according to ASTM D6579-11 (“Standard Practice for Molecular Weight Averages and Molecular Weight Distribution of Hydrocarbon, Rosin and Terpene Resins by Size Exclusion Chromatography”. UV detector; 254nm, solvent: unstabilised THF, retention time marker: toluene, sample concentration: 2mg/ml).
• glass transition temperature is a theoretical value, being the glass transition temperature as calculated by the method of Fox on the basis of monomer composition of the monomer charge according to T. G. Fox, Bull. Am. Phys. Soc. (Ser. II) 1, 123 (1956) and J. Brandmp, E. H. Immergut, Polymer Handbook 3 rd edition, John Wiley, New York, 1989.
• substantially free means that the component is present, if at all, in an amount of less than 5% by weight, based on the total weight of the slurry composition.
• the term essentially free means that the component is present, if at all, in an amount of less than 1% by weight, based on the total weight of the slurry composition.
• the term completely free means that the component is not present in the slurry composition, i.e., 0.00% by weight, based on the total weight of the slurry composition.
• total solids refers to the non-volatile components of the binder and/or slurry composition and specifically excludes the organic medium.
• the term “residue of’ when referring to the composition of a polymer refers to a singular molecular unit within the polymer that results from incorporation (i.e., reaction) of a monomer during polymerization.
• the term “consists essentially of’ includes the recited material or steps and those that do not materially affect the basic and novel characteristics of the binder composition, slurry composition, electrode, or electrical storage device.
• each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
• a closed or open-ended numerical range is described herein, all numbers, values, amounts, percentages, subranges and fractions within or encompassed by the numerical range are to be considered as being specifically included in and belonging to the original disclosure of this application as if these numbers, values, amounts, percentages, subranges and fractions had been explicitly written out in their entirety.
• TEP triethyl phosphate
• the monomer solution was added into flask via an addition funnel over 300 minutes. After the monomer feed was complete, the monomer addition funnel was rinsed with 12.4 grams of TEP. After the initiator feed was complete, the initiator addition funnel was rinsed with 12.4 grams of TEP. The reaction was then held at 120°C for 60 minutes. After the 60-minute hold, the reaction was cooled and poured into a suitable container. The final measured solids of the resin was determined to be 51.0% solids.
• the solids content of the (meth)acrylic polymers were measured in each (meth)acrylic polymer example by the following procedure: An aluminum weighing dish from Fisher Scientific, was weighed using an analytical balance. The weight of the empty dish was recorded to four decimal places. Approximately 0.5 g of dispersant was added to the weighed dish and the weight of the dish and the (meth)acrylic polymer solution was recorded to four decimal places. Next approximately 3.5 g of acetone was added to the weighing dish. The dish containing the (meth)acrylic polymer solution and acetone was placed into a laboratory oven, with the oven temperature set to 110 degrees centigrade, and dried for 1 hour. The dish and dried (meth)acrylic polymer were weighed using an analytical balance.
• the weight of the dish and dried (meth)acrylic polymer was recorded to four decimal places.
• TEP triethyl phosphate
• the monomer solution was added into flask via an addition funnel over 300 minutes. After the monomer feed was complete, the monomer addition funnel was rinsed with 12.4 grams of TEP. After the initiator feed was complete, the initiator addition funnel was rinsed with 12.4 grams of TEP. The reaction was then held at 125°C for 60 minutes. After the 60- minute hold, the reaction was cooled and poured into a suitable container. The final measured solids of the resin was determined to be 51.0% solids.
• TEP triethyl phosphate
• the monomer solution was added into flask via an addition funnel over 300 minutes. After the monomer feed was complete, the monomer addition funnel was rinsed with 12.4 grams of TEP. After the initiator feed was complete, the initiator addition funnel was rinsed with 12.4 grams of TEP. The reaction was then held at 120°C for 60 minutes. After the 60-minute hold, the reaction was cooled and poured into a suitable container. The final measured solids of the resin was determined to be 51.0% solids.
• a dispersion of PVDF was prepared in a mixture of TEP and EAA by the addition of resin A, resin B, resin C, PVDF 1, and PVDF 2 on a 12.2-gram scale.
• a total of 403 mg of (meth)acrylic polymer and 1.26 grams of PVDF were used to make the binder dispersion, “Bl”.
• the weight ratio of (meth)acrylic polymer was 2.0 parts resin A to 1.0 part resin B to 1.2 parts resin C.
• the weight ratio of PVDF was 1.86 parts PVDF 1 to 1.00 parts PVDF 2.
• the PVDF dispersion was prepared in two parts. The first part was prepared by the addition of resin C to 9.46 grams of TEP under high shear mixing. To this mixture was added PVDF 2.
• PVDF solution (inventive binder) - binder solution B2
• a PVDF solution was prepared by dissolving resin A, resin B, resin C, PVDF 1, and PVDF 2 in TEP under high shear mixing using a Cowles blade on a 100-gram scale according to the follow procedure.
• a total of 2.20 grams of (meth) acrylic polymer and a total of 6.86 grams of PVDF were used in the preparation of binder solution “B2”.
• Resin A, resin B, and resin C were all added to 90.95 grams of TEP and agitated until dissolved.
• PVDF 1 was added to the solubilized (meth)acrylic polymer in two portions.
• Binder solution B2 had a total solids of 8.0% (by weight).
• the binder solution was diluted with TEP or a mixture of TEP/EAA and added to a Thinky cup.
• conductive carbon was added and mixed with a wooden blade by hand.
• the Thinky cup was capped and removed from the glove bag.
• Dispersion of the carbon was achieved using a centrifugal mixer. Once homogenous, the carbon slurry was returned to the glove bag, uncapped, and the active material was added.
• the active material/carbon slurry was mixed by hand using a wooden blade, capped, and removed from the glove bag. Dispersion of the active material was achieved using a centrifugal mixer. Once homogenous, the carbon/active material slurry was returned to the glove bag, uncapped, and the additive solution was added.
• the fully formulated positive electrode slurry was mixed by hand using a wooden blade, capped, and removed from the glove bag. Final dispersion of all of the positive electrode slurry components was completed using a centrifugal mixer.
• This slurry was prepared on a 101.1-gram scale with a weight ratio of 95% active material to 3% conductive carbon to 2% binder.
• Table 1 provides the exact weights of the components used in the preparation of slurry SI according to method 1. The weight% solids of the slurry was 73%.
• Electrode films cast from slurry S 1 and slurry S2 were prepared using a 200 micron draw down bar on a draw down table onto aluminum foil. Then, the deposited films were oven-dried for two minutes at 80°C then for four minutes at 120°C. Each film was pressed using a calendar press to a porosity of 33% resulting in a film thickness ranging from 63 to 65 microns. The coating weight of the deposited positive electrode was 20.4 mg/cm 2 from slurry SI and 20.6 mg/cm 2 from slurry S2.
• NMP Distilled N-methylpyrrolidone
• Positive electrode slurries were prepared at room temperature (23 °C) with a humidity of 45-55% (not in a dry bag).
• the binder B2 or PVDF 2
• the diluent TEP or NMP
• conductive carbon was added and mixed with a wooden blade by hand. Dispersion of the carbon was achieved using a centrifugal mixer. Once homogenous, the active material was then added. The active material/carbon slurry was mixed by hand using a wooden blade. Dispersion of the active material was achieved using a centrifugal mixer. Once homogenous, the additive solution Z was added, where noted.
• the fully formulated positive electrode slurry was mixed by hand using a wooden blade.
• Electrode films cast from slurry S3 and slurry S4 were prepared (cast and dried) in the same manner as described in Example 1. Films cast from slurry S3 and slurry S4 were pressed using a calendar press to a porosity of 30-35% resulting in a film thickness ranging from 55 to 65 microns. The coating weight of the deposited film was approximately 20 mg/cm 2 for each electrode film.
• the TEP-based binder B2 used to make S3 electrodes demonstrated comparable adhesion strength compared to the standard PVDF in NMP binder.
• the TEP-based binder B2 could be made at higher solids content than the NMP-based binder, and TEP has less health and environmental risk than NMP.
• Binder dispersion B3 was prepared in a mixture of TEP and EAA in a manner analogous to binder dispersion B 1 in example 1 using the same (meth)acrylic polymer weight ratios and PVDF weight ratios.
• Binder solution B4 was prepared in TEP in a manner analogous to binder solution B2 in example 1 using the same (meth)acrylic polymer weight ratios and PVDF weight ratios.
• binder solutions in TEP were prepared in a manner analogous to binder solution B2 in example 1 with different (meth)acrylic polymer weight ratios and different PVDF weight ratios than Binder solution B2.
• the exact weight ratios of (meth)acrylic polymer and exact weight ratio of PVDF are found in Table 5 normalized to 100% of the total solids based on weight.
• Binder solutions B5, B6, B7, B8, and B9 all were prepared at 8.0% total solids by weight.
• Method 3 General procedure for the preparation of positive electrode slurries for Example 3 [00159]
• the binder solution was diluted with NMP, TEP or a mixture of TEP/EAA and added to a Thinky cup.
• conductive carbon was added and mixed with a wooden blade by hand.
• the Thinky cup was capped and removed from the glove bag. Dispersion of the carbon was achieved using a centrifugal mixer. Once homogenous, the carbon slurry was returned to the glove bag, uncapped, and the active material was added. The active material/carbon slurry was mixed by hand using a wooden blade, capped, and removed from the glove bag. Dispersion of the active material was achieved using a centrifugal mixer.
• PVDF -dispersion positive electrode slurry S12 This positive electrode slurry was prepared in a manner analogous to slurry S 1 according to method 3 (and included additive solution Z). Binder composition B3 was used to formulate slurry Sll. This slurry was prepared with a weight ratio of 95% active material to 3% conductive carbon to 2% binder based on the total solids (not including the additive solution Z). The weight % solids of the slurry was 73% based on total weight of the composition.
• Electrode films cast from slurries S5 to S12 were prepared (cast and dried) in the same manner as described in Example 1. Films cast from slurry S5 to slurry S12 were pressed using a calendar press to a porosity of 30-35% resulting in a film thickness ranging from 55 to 65 microns. The coating weight of the deposited film was approximately 20 mg/cm 2 for each electrode film.
• Binder dispersion B 13 was prepared in a mixture of TEP and EAA in a manner analogous to binder dispersion B 1 in example 1 using the same (meth)acrylic polymer weight ratios and PVDF weight ratios. Binder dispersion B 13 had a total solids of 8.0% (by weight) and a viscosity of 202 cP at a shear rate of 10 per second using the method described above.
• Binder solution B 14 was prepared in TEP in a manner analogous to binder solution B2 in example 1 using the same (meth)acrylic polymer weight ratios and PVDF weight ratios. Binder solution B14 had a total solids of 8.1% (by weight) and a viscosity of 1161 cP at a shear rate of 10 per second using the method described above.
• Binder solution B 15 was prepared in a manner analogous to Binder solution B2 in example 1 except all of the PVDF in the composition was PVDF 2. Binder solution B 15 had a total solids of 8.6% (by weight) and a viscosity of 3337 cP at a shear rate of 10 per second using the method described above.
• Binder solution B 16 was prepared in a manner analogous to Binder solution B2 in example 1 except no (meth)acrylic polymer was used and all of the PVDF in the composition was PVDF 2. Binder solution B 16 had a total solids of 7.9% (by weight) and a viscosity of 6345 cP at a shear rate of 10 per second using the method described above.
• Additive solution Z was added at the same level as in slurry S2 but was not included in the calculation in Table 11 for slurry compositions S13, S14, and S15. Additive solution Z was not added in Slurry S16.
• Electrode films cast from slurries S 13 to S 16 were prepared (cast and dried) in the same manner as described in Example 1. Films cast from slurry S13 to slurry S16 were pressed using a calendar press to a porosity of 30-35% resulting in a film thickness ranging from 55 to 65 microns. The coating weight of the deposited film was approximately 20 mg/cm 2 for each electrode film.
• Adhesion testing for positive electrode films resulting from slurries S 13 to S 16 was conducted in the same manner as described in example 1.
• the average peel strength is shown in Table 12 below.

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